Energy effective production of lime products comparing industrial and scientific laboratory methods for prediction.

By Olof Sandstrm, PhD Olof Sandstrm, Graptolit Geoproject AB, Kapellgatan 10, SE-214 21 Malm, Sweden. olof@graptolitgeo.se. limestone dips to the southeast (0.15- 0.3; Erlstrm et al 2009). The project Energy-effective production of lime products The Stucks area is situated in the northernmost part of Gotaims to predict the thermal behavior and degeneration of limeland (Fig. 1). Here, pure limestones dominate, marls occur on stones and dolomites when calcinated to lime and dolime. The the surface only as minor pockets. The limestone has a general project consist of three parts: 1) Explain the causes of thermal thickness of ca 30 50 m, below is marls and marly limedeterioration, 2) Develop methods for prediction and 3) Implestones. Quarrying in the area has a long history, beginning in mentation of the results to the industry. This report is a part of the early 1900s. In 1997 SMA Mineral AB re-opened the the third stage, describing and comparing an implementation quarry as a part of a lime kiln purchase in Oxelsund. The attempt with the methods used in laboratory scale. quarry has been steadily increasing its volumes and is now mining ca 1 million tons of high purity limestone every year. The limestone is divided into crinoid limestone, fragmeneted Geology of Gotland limestone, reef limestone and stromatoporoid limestone. FragThe Gotland bedrock consists of limestone, marlstone and mented limestones and crinoid limestones usually form the sandstone geographically distributed according to Figure 1. base for the development of the reef limestone (cf. Fig 2). Reef The bedrock is predominately from the early to mid-Silurian limestones are build-ups of reef forming organisms, in this case period about 430 million years ago when the Baltic Sea was a shallow tropical sea located close to the Equator (Erlstrm et al corals and stromatoporoids (a sponge that was the dominant reef-building organism during the Silurian period). This reef 2009). The Silurian strata of the island have its oldest parts in the NW and the youngest in the S and have not been subjected build-up is flanked by debris in the form of crinoid limestones and fragmented limestones. On the top, a layered build-up of to any greater compaction or heating. The strike of the sedistromatoporoids forms the stromatoporoid limestone (Fig 2). mentary limestone is dominantly northeast/southwest and the

Introduction

Fig. 1. Map of Gotland with the distribution of the main lithological facies (from Sandstrm 1998). The photograph shows the area of Stucks limestone deposit and quarry.

Fig. 2. A generalized facies model for the most common lithostratigraphic succession on northern Gotland. The thickness of such a unit varies between 15m and 60 m.

Fig. 3. Geologic profile, chemistry and thermal results of the two methods of DH 1. The letters a j refers to example photographs of different facies in Fig 4. Thickness of the right hand side of the lithological column refers to the system by Dunham (1962) and the letters at the bottom of the column are: m= mudstone; w=wackestone; p=packstone; g=grainstone; b=boundstone.

Fig. 4. Photographs showing the different facies of DH 1. The position of each picture is indicated by its corresponding letter in Fig. 3. a. Crinoid limestone (grainstone) with abundant stylolites. b. Fragmented limestone (packstone). c. Stromatoporoid limestone (boundstone) intercalated with fragmented limestone (packstone). d. Reefal fragmented limestone (packstone). e. Stromatoporoid limestone (boundstone). f. Crinoid limestone, partly with micritic matrix (packstone/ grainstone). g. Fragmented limestone with solitary rugose corals and coated grains (wackestone/packstone). h. Reef limestone (boundstone), partly rich in stromatoporoids. i. Crinoid limestone with abundant stylolites and fine clay intercalations (grainstone). j. Fragmented marly limestone, with abundant fossil fragments and in part rich in crinoids (storm depositions; packstone).

Methods
Limestone classification follows Dunham (1962) and the nomenclature used for this project (marl, crinoid limestone, fragmeneted limestone, reef limestone and stromatoporoid limestone). For the project a laboratory scale kiln was built at Lund University, and a method for measuring the thermal detoriation was developed. This method is however not really applicable for a large sample size with high throughput. A method developed by SMA Mineral AB can use coarse +1cm fractioned limestone with faster throughput, since more samples per time unit can be handled. The question is whether the two methods are comparable, and whether they yield similar results. In an attempt to im-

plement and model the Stucks reserve for thermal detoriation a comparative test was made on two selected drill cores from the area. The method developed by Lund University will here be referred as the Lund-method and the method developed by SMA Mineral AB will be referred as the SMA-method. The SMA-method. Approximately 2 kg limestone is crushed in a jaw crusher with CSS=1cm. The sample is sieved on 5mm and 10mm. 500g (0,1g) of the 5/10 fraction with equal over and under- size portion, is placed in a ceramic bowl and heated with an even increase to 1150C in 240 minutes. 1150C should be reached within 60 minutes. After 240 minutes, the kiln is shut off and the sample is slowly cooling down until it is cool enough to be

Fig. 5. Geologic profile, chemistry and thermal results of the two methods of DH 2. The letters a i refers to example photographs of different facies in Fig 6. Thickness of the right hand side of the lithological column refers to the system by Dunham (1962) and the letters at the bottom of the column are: m= mudstone; w=wackestone; p=packstone; g=grainstone; b=boundstone.

placed in an exicator. The entire sample is weighted (m1). Then it is carefully sieved by hand on a 5mm sieve. All of the sample on the sieve must be in contact with the sieve-cloth. Weigh the +5mm sample (m2). The thermal detoriation is then the percentual difference between the two weighted samples:

is shaken for 1 minute with amp.=2,5 and after that for 2 minutes with amp.=1,5. Before burning, after burning and after each shake the number of pieces larger than 8mm are counted. Before sieving, each sieve is weighted separately. After the last sieving procedure, each sieve with material is weighted and the actual sieve weight is deducted (m8mm, m4mm, m2mm). The total amount of fines is the sum of material that has passed the 8mm sieve.

% thermal detoriation =

% thermal detoriation =

The Lund-method A core sample is weighted (m1) and then placed in a ceramic furnace and slowly heated to 1050C. The top temperature is held for 4 hours and is the cooled down slowly. When the temperature of the sample cooled enough to be managed it is placed in a sealed container to avoid moisture and CO2 exposure. The sample is removed from the container and placed in a vibratory sieve shaker with 8, 4 and 2 mm sieves. The sample

Shatter tests The shatter test is a standard way to test thermal detoriation in kilns and is used by kiln manufacturers to test whether their kiln is suitable for the intended material or not. There are several varieties and each manufacturer has their own version of the method. The problem with these methods is that they do not

Fig. 6. Photographs showing the different facies of DH 2. The position of each picture is indicated by its corresponding letter in Fig. 5. a. Stylolite-rich crinoid limestone (grainstone). b. Crinoid limestone with fine clay intercalations (grainstone). c. Crinoid limestone (partly fragmented limestone) rich in stylolites (packstone/grainstone). d. Fine-grained limestone, partly fragmented limestone (wackestone). e. Reef limestone (boundstone). f. Fragmenetd limestone with micritic matrix, partly rich in crinoids (wackestone/packstone). g. Coarse crinoid limestone rich in stylolites (grainstone). h. Fragmeneted limestone rich in crinoids and stylolites (storm layer; packstone). i. Nodular marl with intercalations of storm deposited fragmented limestone (wackestone/packstone).

seem to be too reliable. If the method says OK, then it is OK, but when the method says not OK, it is still OK in about half of the cases according to my own experience. Another problem is that they require relatively large sample size. I will give a general description of how shatter tests are made. From the sample one or more cubes are cut, normally about 1dm3 each. The cubes are weighted, placed in a furnace and heated to a temperature suitable for the kiln per see. After the heating process, the cube(s) are placed in a tumbler or shaker and mishandled for some time. After tumbling process, the material is sieved and each fraction is weighted. Depending on manufacturer and type of use, different sieves sizes are used. Results from shatter tests are to some extent comparable to the methods tested in this report. However, shatter tests are normally much more expensive, and are suitable for very few samples to test the kilns suitability for a certain finding. The

method is not suitable for quantification and very large amount of samples.

Results
Two drillcores DH1 and DH 2 was selected for a detailed
examination. They were described geologically and samples were taken for analysis of thermal detoriation in the Lund laboratory. Already jaw-crushed material from a previous chemical test was available and was used for the SMA-method. This material was collected in 2m intervals. DH 1 (fig 3) is 40,97 m deep. It begins with a marly fragmeneted limestone (packstone; Fig 4j) partly rich in crinoids followed by a stylolite-rich crinoid limestone (grainstone; Fig 4i), a reef limestone with abundant stromatoporoids (boundstone; Fig 4h), a fragmented limestone, with finegrained

Fig. 7. Comparision of the result from DH 2 of the two methods. Black curve is the result from the Lund-method with a moving average of 4. Gray curve is the result from the SMA-method. The curves generally follows the same pattern and with similar magnitude.

Fig. 8. Comparision of the result from DH of the two methods. Here the average of each 2 m interval of the Lund-method (black curve) is compared with the SMA-method (gray curve) The result from this comparision show that the methods are probably comparable, with very similar outcome.

matrix and partly abundant in solitary rugose corals (wackestone/packstone; Fig 4g), a crinoid limestone with partly micritic matrix (packstone/grainstone; Fig 4f), Fragmented limestones (packstones, Fig 4b, d) intercalated with stromatoporoid limestones (boundstones; Fig 4c, e). On top is a crinoid limestone with abundant stylolites (grainstone; Fig 4a). CaO and SiO2 values follow the micritic content (i.e. Dunham classification), more micrite gives higher SiO2 and lower CaO (cf. Fig 3 Dunham classification and the chemical curves). The % fines curves from the two methods look somewhat different. This is because of sampling interval. About 4 times denser sampling interval for the Lund-method compared to the SMAmethod yields a more spiky looking curve for the Lund data. If, however you look at the more large-scaled cyclicity of the Lund data, one can see that there is a correlation.

DH 2 (Fig 5) is exactly 40m deep. This sequence begins with nodular marl that coarsens upwards to a fragmented limestone with a high degree of micritic matrix (mudstone/wackestone/ packstone; Fig 6i, h). This is followed by a crinoid limestone rich in stylolites (grainstone; Fig 6g), a fragmented limestone, partly crinoid-rich (wackestone/packstone; Fig 6f), a reef limestone (boundstone; Fig 6e), a finegrained limestone, partly fragmental (wackestone; Fig 6d), a fragmented limestone with minor stylolites (wackestone/packstone; Fig 6c), and ending with a stylolite-rich crinoid limestone (packstone/grainstone; Fig 6a, b, c). Here too, the CaO and SiO2 curves seem to follow the micritic content, although it is not as obvious as in DH 1. Also, the two % fines-curves show the same pattern and general similarities as for the DH 1.

Correlating the methods In order to see how good the two methods correlate, the two curves from the DH 2 was compared. In order to smoothen the Lund-data a moving average filter was applied with a four sample mean. This smoothens the curve a bit and dampens the variation. Comparing the two curves in the same diagram shows a very good general correlation between the two (Fig 7). A second way to check the correlation of the two is to make fewer samples of the Lund-method by averaging every 2 meters. This gives a very smooth curve, almost identical with the curve from the SMA-method (Fig 8).

Discussion and Conclusions

The two methods seem to correlate well with each other,
making the SMA-method a good choice for further industrial testing and modeling. In an older report from SMA (Grsberg unpublished), correlation between shatter tests and the SMAmethod was proven. However, the shatter test showed generally higher values compared to the SMA-method. In previous case studies from the project (Sandstrm, 2011) a good correlation between lithology type and thermal detoriation was evident. However, here it is not the case. Looking at the data, there seem to be a weak negative correlation to SiO 2content and a weak positive correlation to stylolite frequency. Hatched areas in Fig 8 shows where stylolites are abundant. A third alternative is microfacies and micritic content that may correlate as well. Looking at figures 3 and 5 a correspondence between grainstone and increase in thermal detoriation is possible. Sandstrm & Calner (2011) shows in an example from the same area the importance of deep geological knowledge in order to find, plan and produce correct qualities of limestone. Here a systematic approach is used that has been developed by Thomas Aigner (eg. Pawellek & Aigner 2004), called Dynamic Stratigraphy and involves a systematic analysis of rock sequences along a hierarchy of spatial and temporal scales from microfacies analysis to larger scaled sequence- and stack-

ing analysis. Correct knowledge of the mechanisms behind the thermal behavior is of essence for the dynamic understanding of the relation between depositional environment, tectonics and burial history if the carbonate rock. The good correlation between the two methods does, however mean that one is able to model and selectively quarry on thermal quality even when the background knowledge is limited. However, one will need to use denser sampling and a denser array of drillings to get good accuracy in the model. With a good knowledge on the causes of thermal detoriation one can make correct correlations to other parameters (such as chemistry, lithology or texture), and obtain a good precision with less laboratory work. One example of this is the casemodel presented in Sandstrm (2011).

References
Dunham, R.J., 1962: Classification of carbonate rocks according to depositional texture. In W.E. Ham (ed.): Classification of carbonate rocks, 108121. American Association of Petroleum Geologists, Memoir 1. Erlstrm, M., Persson, L., Sivhed, U. & Wickstrm, L., 2009: Beskrivning till regional berggrundskarta ver Gotlands ln. SGU serie K 221, 66pp. Pawellek, T. & Aigner, T., 2004: Dynamic stratigraphy as a tool in economic mineral exploration: ultra-pure limestones (Upper Jurassic, SW Germany). Marine and Petroleum Geology 21, 499-516. Sandstrm, O., 1998: Sediments and stromatoporoid morphotypes in Ludfordian (Upper Silurian) reefal sea stacks on Gotland, Sweden. GFF 120, 365371. Sandstrm, O., 2011 (in press): Energy-effective production of lime products Case models. MinFo Publications no. xxxx, xxpp. Sandstrm, O. & Calner, M., 2011 (in ms): A model for northern Gotland high purity limestones based on a Dynamic Strati-graphic concept . MinFo Publications no xxx, xxpp.